FI69620B - CATALYTIC CONTAINER FOR THE FRAME STATION OF VETGAS AND THREE METALS - Google Patents
CATALYTIC CONTAINER FOR THE FRAME STATION OF VETGAS AND THREE METALS Download PDFInfo
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- FI69620B FI69620B FI842175A FI842175A FI69620B FI 69620 B FI69620 B FI 69620B FI 842175 A FI842175 A FI 842175A FI 842175 A FI842175 A FI 842175A FI 69620 B FI69620 B FI 69620B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Description
69620 1 Katalysaattori ja menetelmä vetykaasun valmistamiseksi hiilimonoksidista ja vedestä69620 1 Catalyst and process for the production of hydrogen gas from carbon monoxide and water
Katalysator och förfarande för framställning av vätgas ur kolmonoxid och vatten 5Catalyst and reflux catalyst for the production of carbon monoxide and water 5
Keksinnön kohteena on katalysaattori vetykaasun valmistamiseksi hiilimonoksidista ja vedestä. Keksinnön kohteena on myös menetelmä vetykaasun 10 valmistamiseksi hiilimonoksidista ja vedestä katalysaattorin läsnäollessa.The invention relates to a catalyst for the production of hydrogen gas from carbon monoxide and water. The invention also relates to a process for the preparation of hydrogen gas 10 from carbon monoxide and water in the presence of a catalyst.
Vesikaasun siirtoreaktiota CO + H^O käytetään vedyn valmistuk seen ja synteesikaasun vetypitoisuuden kohottamiseen. Tärkeimpiä teollisia 15 sovellutusalueita ovat vedyn valmistaminen, Fischer-Tropsch synteesi ja ara-moniakkisynteesi. Reaktio on eksoterminen, joten suurin konversio tasapainossa saavutetaan alhaisessa lämpötilassa. Paine ei vaikuta tasapainoon.The water gas transfer reaction CO + H 2 O is used to produce hydrogen and to increase the hydrogen content of the synthesis gas. The main industrial 15 applications are hydrogen preparation, Fischer-Tropsch synthesis and ara-polyacia synthesis. The reaction is exothermic, so maximum conversion at equilibrium is achieved at low temperature. The pressure does not affect the balance.
Reaktion heterogeenisina katalysaattoreina käytetään metallioksidiseok-20 siä (Scatterfield: Heterogeneous Catalysis in Practice, McGraw Hill 1980). Korkeassa lämpötilassa 325-550°C toimivassa prosessissa käytetään rautaoksidin Fe^O^ ja kromioksidin C^O^ seosta. Korkea lämpötila on välttämätön riittävän reaktionopeuden saavuttamiseksi. Paine on prosessissa noin 3 MPa. Katalysaattorin toimintalämpötilassa reaktiotasapainossa on hiilimonoksi-25 dia, joka täytyy poistaa esimerkiksi ammoniakkisynteesissä.Metal oxide mixtures (Scatterfield: Heterogeneous Catalysis in Practice, McGraw Hill 1980) are used as heterogeneous catalysts for the reaction. The high temperature process of 325-550 ° C uses a mixture of iron oxide Fe 2 O 2 and chromium oxide C 2 O 2. A high temperature is necessary to achieve a sufficient reaction rate. The pressure in the process is about 3 MPa. At the operating temperature of the catalyst, there is carbon monoxy-25 dia in the reaction equilibrium, which must be removed, for example, in ammonia synthesis.
Vesikaasun siirtoreaktiooon on kehitetty myös matalammassa lämpötilassa toimivia katalysaattoreita, joita käytetään korkealämpÖtilakatalyysin yhteydessä. Nämä katalysaattorit sisältävät kuparioksidia CuO, sinkki-30 oksidia ZnO ja alumiinioksidia A^O^. Käyttölämpötila on noin 200°C ja paine 1,3 MPa.Lower temperature catalysts have also been developed for the water gas transfer reaction and are used in connection with high temperature catalysis. These catalysts contain copper oxide CuO, zinc oxide ZnO and alumina N 2 O 2. The operating temperature is about 200 ° C and the pressure 1.3 MPa.
Molemmat katalysaattorityypit ovat pyrofoorisia ja siksi niitä täytyy käsitellä hapettomissa oloissa.Both types of catalyst are pyrophoric and therefore must be treated under anaerobic conditions.
Vesikaasun siirtoreaktion katalyysi voidaan saada aikaan myös homogeenisilla katalysaattoreilla liuoksessa alhaisessa paineessa ja lämpötilaa- 35 2 69620 1 sa. Katalysaattoreina toimivat esimerkiksi rodium- ja iridiumkarbonyylijo-didit (US-patentti n:o 4.151.107 ja US-patentti n:o 4.107.076) sekä muut ryhmän VIII metalliyhdisteet (US-patentti n:o 3.490.872 ja US-patentti n:o 3.539.298).Catalysis of the water gas transfer reaction can also be accomplished with homogeneous catalysts in solution at low pressure and temperature. Examples of catalysts are rhodium and iridium carbonyl iodides (U.S. Patent No. 4,151,107 and U.S. Patent No. 4,107,076) and other Group VIII metal compounds (U.S. Patent No. 3,490,872 and U.S. Pat. : o 3,539,298).
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Tunnettujen homogeenisten katalysaattorien teollisen soveltamisen on estänyt niiden alhainen aktiivisuus.The industrial application of known homogeneous catalysts has been hampered by their low activity.
Keksinnön päämääränä on aikaansaada parannus edellä esitettyihin epäkoh-10 tiin. Keksinnön yksityiskohtaisempana päämääränä on aikaansaada katalysaattori vetykaasun valmistamiseksi hiilimonoksidista ja vedestä, joka katalysaattori on huomattavasti parempi aikaisemmin tunnettuihin vastaaviin katalysaattoreihin nähden.It is an object of the invention to provide an improvement over the above drawbacks. It is a more detailed object of the invention to provide a catalyst for the production of hydrogen gas from carbon monoxide and water, which catalyst is considerably superior to the corresponding catalysts previously known.
15 Keksinnön päämäärät saavutetaan katalysaattorilla, jolle on pääasiallisesti tunnusomaista se, että katalysaattori on valmistettu ryhmän VIII metallikarbonyylistä, jonka kaava onThe objects of the invention are achieved by a catalyst which is mainly characterized in that the catalyst is made of a Group VIII metal carbonyl of the formula
M, M' (CO).. L + y BM, M '(CO) .. L + y B
3-n n 12-x x y 20 jossa H = Ru M' = Fe n on 0, 1 tai 2 25 x on 0, 1 tai 2 L on triaryyli tai trialkyyli fosfiini tai fosfiitti B on kelatoituva kaksihampainen heterosyklinen typpeä sisältävä emäs y on kokonais- tai murtoluku välillä 1-6.3-nn 12-xxy 20 where H = Ru M '= Fe n is 0, 1 or 2 x x is 0, 1 or 2 L is triaryl or trialkyl phosphine or phosphite B is a chelating bidentate heterocyclic nitrogen-containing base y is or a fraction between 1-6.
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Ryhmän Vili metallikarbonyyli on Ru^(CO)^» 12’ ^^RuCCO)^ ta* niiden johdannainen M^iCO)^ XLX» j°ssa M on Ru tai Fe, x = 1 tai 2 ja L = trialkyyli tai triaryylifosfiini tai -fosfiitti.The metal carbonyl of the group Vili is Ru (CO) ^ »12 '^ ^ RuCCO) ^ ta * their derivative M ^ iCO) ^ XLX» j ° M is Ru or Fe, x = 1 or 2 and L = trialkyl or triarylphosphine or phosphite.
Patenttivaatimuksen 3 mukaisesti heterosyklinen emäs on 2,2'-bipyridiini tai 1,10-fenantroliini.According to claim 3, the heterocyclic base is 2,2'-bipyridine or 1,10-phenanthroline.
Il 35 3 69620 1 Keksinnön päämääränä on myös aikaansaada parannus menetelmään vetykaasun valmistamiseksi hiilimonoksidista ja vedestä katalysaattorin läsnäollessa.Il 35 3 69620 1 It is also an object of the invention to provide an improvement in a process for the production of hydrogen gas from carbon monoxide and water in the presence of a catalyst.
5 Keksinnön mukaiselle menetelmälle on pääasiallisesti tunnusomaista se, että katalysaattorina käytetään patenttivaatimuksen 1, 2, 3 tai 4 mukaista karbonyyliyhdistettä suspensiona vesiliuoksessa tai kantaja-aineeseen sidottuna.The process according to the invention is mainly characterized in that the catalyst used is a carbonyl compound according to claim 1, 2, 3 or 4 in the form of a suspension in aqueous solution or bound to a support.
10 Keksinnön mukaisen menetelmän muut tunnuspiirteet on esitetty patenttivaatimuksessa 4.Other features of the method according to the invention are set out in claim 4.
Katalysaattori, joka sisältää ruteenikarbonyyliä tai sen johdannaista ja bipyridiiniä tai vastaavaa heterosyklistä typpiyhdistettä, nopeuttaa 15 reaktiota tehokkaammin alhaisessa lämpötilassa ja paineessa kuin aikaisemmat katalysaattorit. Reaktionopeus saadaan kohotettua jo alhaisessa lämpötilassa 80-l50°C ja paineessa 0,04-0,2 MPa. Reaktion energiataloutta voidaan merkittävästi parantaa ja laitteistoja yksinkertaistaa. Seuraavassa selvitetään keksintö yksityiskohtaisesti.A catalyst containing ruthenium carbonyl or a derivative thereof and a bipyridine or a corresponding heterocyclic nitrogen compound accelerates the reaction more efficiently at low temperature and pressure than previous catalysts. The reaction rate can be increased even at a low temperature of 80-150 ° C and a pressure of 0.04-0.2 MPa. The energy economy of the reaction can be significantly improved and the equipment simplified. The invention will now be described in detail.
2020
Keksintö perustuu havaintoihin ruteenikarbonyylin Ru^CCO)^ ja 2,2'-bipyridiinin reaktioista hiilimonoksidissa. Nämä lähtöaineet muodostavat noin 80-100°C lämpötilassa ja 0,05 MPa:n paineessa sinisen ilmaherkän ja orgaanisiin liuottimiin niukkaliukoisen yhdisteen. Tämä tuote, joka 25 on ruteenia ja 2,2'-bipyridiiniä sisältävä karbonyyliyhdiste katalysoi vesikaasun siirtoreaktiota sekä kaasufaasissa että suspensiona liuosfaa-sissa. Ruteenikarbonyylin ja 2,2'-bipyridiinin katalyysiominaisuuksia vesikaasunsiirtoreaktiossa on aikaisemmin raportoitu (Choudbury & Cole-Hamilton J.Chem.Soc. Dalton Trans. 1885, 1982), mutta tutkimuksessa on 30 kyse homogeenisesta fotokatalysaattorista, jossa katalysaattorit sisältävät klooria. Tässä keksinnössä esitetty katalysaattori on aktiivisuudeltaan kertaluokkaa suurempi aikaisempia vastaavissa oloissa toimivia katalysaattoreita. Ru^CO)^ Ja 2,2'-bipyridiinin lisäksi on havaittu myös FeRl^iCO)^ ja Fe2Ru(C0)^2 sekä näiden fosfiini- ja fosfiittijoh-35 dannaisten toimivan katalysaattorin lähtöaineena. F.mäksenä toimii myös substituoidut 2,2'-bipyridiinit ja vastaavat fenantroliiniyhdisteet. Seuraavissa esimerkeissä kuvataan katalysaattorin valmistus ja katalyy- h 69620 1 siominaisuudet vesikaasun siirtoreaktiossa.The invention is based on the findings of the reactions of ruthenium carbonyl (CH 2 Cl 2) and 2,2'-bipyridine in carbon monoxide. At a temperature of about 80-100 ° C and a pressure of 0.05 MPa, these starting materials form a blue air-sensitive compound which is sparingly soluble in organic solvents. This product, a carbonyl compound containing ruthenium and 2,2'-bipyridine, catalyzes the aqueous gas transfer reaction both in the gas phase and as a suspension in the solution phase. The catalytic properties of ruthenium carbonyl and 2,2'-bipyridine in a water gas transfer reaction have been previously reported (Choudbury & Cole-Hamilton J. Chem. Soc. Dalton Trans. 1885, 1982), but the study is about a homogeneous photocatalyst in which the catalysts contain chlorine. The catalyst of the present invention is one order of magnitude more active than prior art catalysts. In addition to Ru 2 CO) and 2,2'-bipyridine, FeR 1, CO 2 and Fe 2 Ru (CO) 2 and these phosphine and phosphite derivatives have also been found to serve as catalyst catalysts. Substituted 2,2'-bipyridines and the corresponding phenanthroline compounds also function as a base. The following examples illustrate the preparation of the catalyst and the properties of the catalyst in the water gas transfer reaction.
Esimerkki IExample I
5 Ruteenikarbonyyli Ru^(C0)^2 (0,15 mmoolia) ja 2,2'-bipyridiini (1,0 mmoo-lia) liuotettiin hapettomaan sykloheksaaniin (0,1 dm3). Liuosta refluksoi-taessa 80°C lämpötilassa alkoi noin puolen tunnin kuluttua saostua mustaa kompleksia. Kolmen tunnin kuluttua oli kaikki Ru^iCO)^ reagoinut. Syntynyt sakka suodatetttiin ja pestiin hapettomalla heksaanilla ja vakuumi-10 kuivattiin.Ruthenium carbonyl Ru 2 O (CO 2) 2 (0.15 mmol) and 2,2'-bipyridine (1.0 mmol) were dissolved in oxygen-free cyclohexane (0.1 dm 3). The solution was reflux-appropriate, at a temperature of 80 ° C started after about a half hour to precipitate a black complex. After three hours, all of the Ru 2 O 2 O 3 had reacted. The resulting precipitate was filtered and washed with anhydrous hexane and dried in vacuo.
Esimerkki IIExample II
Kuten esimerkissä I, mutta metallikarbonyyli ja emäs taulukon 1 mukai-15 sesti.As in Example I, but with the metal carbonyl and base according to Table 1.
Taulukko 1table 1
Metallikarbonyyli Emäs 20____________________________Metal Carbonyl Base 20____________________________
Ru^(CO)j2 1,10-fenantroliiniRu ^ (CO) j2 1,10-phenanthroline
FeRu2(CO)^2 2,2’-bipyridiiniFeRu2 (CO) ^ 2 2,2'-bipyridine
Fe2Ru(CO)^2 2,2'-bipyridiini 25 Ru3(CO)11PPh3 2,2’-bipyridiini Näissä reaktioissa muodostuu myös esimerkissä I kuvattua yhdistettä vastaava johdannainen.Fe2Ru (CO) ^ 2 2,2'-bipyridine 25 Ru3 (CO) 11Phh3 2,2'-bipyridine In these reactions, a derivative corresponding to the compound described in Example I is also formed.
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Esimerkki IIIExample III
Katalysaattori voidaan valmistaa myös suoraan kantajan pinnalle seuraavasti: Ruteenikarbonyyli Ru3(CO)^2 (0,15 mmoolia) ja 2,2'-bipyridiini 35 (1,0 mmoolia) liuotettiin dikloorimetaaniin (0,05 dm3). Liuos imeytettiin piigeeliin (3,0 g), jonka jälkeen liuotin haihdutettiin pois evakuoimalla. Imeytettyä geeliä kuumennettiin 100°C lämpötilaan suojakaasussa 69620 1 (CO, tai vakuumissa, jolloin geelin väri muuttuu tumman siniseksi. Geeli aktivoituu katalysaattoriksi 24-48 tunnin aikana 100°C:n lämpötilassa ja 0,05 MPa:n hiilimonoksidipaineessa.The catalyst can also be prepared directly on the support surface as follows: Ruthenium carbonyl Ru 3 (CO) 2 (0.15 mmol) and 2,2'-bipyridine 35 (1.0 mmol) were dissolved in dichloromethane (0.05 dm 3). The solution was absorbed onto silica gel (3.0 g), after which the solvent was evaporated off by evacuation. The absorbed gel was heated to 100 ° C under a shielding gas of 69620 L (CO 2, or in vacuo to give a dark blue color of the gel. The gel is activated as a catalyst for 24-48 hours at 100 ° C and 0.05 MPa carbon monoxide pressure.
5 Esimerkki IV5 Example IV
Esimerkkien I ja II mukainen yhdiste katalysoi vesikaasun siirtoreaktiota 3 seuraavasti: Reaktiopulloon (0,035 dm ) suljettiin kantajaan sitoutunutta kompleksia (0,01 mmoolia, Ru^CO)^ määrän perusteella laskettuna joko 10 vesisuspensiona tai sidottuna kantajaan), vettä (50,0 mmoolia) ja hiilimonoksidia (0,736 mmoolia) sekä metaania sisäiseksi standardiksi. Reaktio-pullo asetettiin öljyhauteeseen lämpötilaan 150°C. Viidentoista minuutin reaktioajan jälkeen lämpötila laskettiin lämpötilaan 25°C ja suoritettiin kaasuanalyysi. Reaktiopullo sisälsi 0,30 mmoolia CO:ta, 0,46 mmoolia 15 C02:ta ja 0,46 mmoolia l^ta. Tuloksen perusteella voidaan laskea katalysaattorin aktiivisuus yksiköissä moolia ^/moolia katalysaattoria x 24 h, jolloin aktiivisuudeksi saadaan 4400.The compound of Examples I and II catalyzes the water gas transfer reaction 3 as follows: The reaction flask (0.035 dm) was sealed with a complex bound to the support (0.01 mmol, based on the amount of Ru and carbon monoxide (0.736 mmol) and methane as an internal standard. The reaction flask was placed in an oil bath at 150 ° C. After a reaction time of 15 minutes, the temperature was lowered to 25 ° C and gas analysis was performed. The reaction flask contained 0.30 mmol CO, 0.46 mmol CO 2 and 0.46 mmol CO 2. Based on the result, the activity of the catalyst in moles / mole of catalyst x 24 h can be calculated, giving an activity of 4400.
Esimerkki VExample V
2020
Koe toistettiin 40 minuutin reaktioajalla, jolloin 0,804 mmoolia CO:ta ja 50 mmoolia H^Oita reagoi antaen 0,77 mmoolia I^ta ja C02:ta. Hiilimonoksidia jäi jäljelle 0,014 mmoolia. Katalysaattorin aktiivisuus oli 2770. Edellistä alempi aktiivisuus johtuu lähtöaineen loppuunkulumisesta. 25 Pitempi reaktioaika johtaa reaktion termodynaamiseen tasapainoon, jossa CO:ta on alle 0,1 moolia %. Reaktiota voidaan jatkaa useita kertoja lataamalla reaktiopullo CO:11a. Katalysaattorin aktiivisuus ei alene merkittävästi perättäisissä kokeissa.The experiment was repeated for a reaction time of 40 minutes, at which time 0.804 mmol of CO and 50 mmol of H 2 O reacted to give 0.77 mmol of H 2 and CO 2. 0.014 mmol of carbon monoxide remained. The activity of the catalyst was 2770. The lower activity is due to the depletion of the starting material. A longer reaction time results in a thermodynamic equilibrium of the reaction with less than 0.1 mole% CO. The reaction can be continued several times by loading the reaction flask with CO. The activity of the catalyst does not decrease significantly in successive experiments.
30 Esimerkki VI30 Example VI
Esimerkin IV mukaisella koejärjestelyllä lämpötilassa 100°C, esimerkkien II mukaisille katalysaattoreille saadaan seuraavat aktiivisuudet 35 69620 1 Taulukko 2The experimental set-up according to Example IV at a temperature of 100 ° C gives the following activities for the catalysts according to Examples II 35 69620 1 Table 2
Metallikarbonyyli Emäs Aktiivisuus (l^) 5Metal Carbonyl Base Activity (l ^) 5
Ru(C0)^2 2,2,-bipyridiini 694Ru (CO) ^ 2 2,2, -bipyridine 694
Fe^RuCCO)^^ 2,2'-bipyridlini 20Fe (RuCCO) -2,2'-bipyridine 20
FeRu^iCO)^ 2,2' -bipyridiini 34 RUjiCO)^ 1,10-fenantroliini 80 10 Ru^iCO) j^PPh^ 2,2'-bipyridiini 65FeRu ^ iCO) ^ 2,2'-bipyridine 34 RURCO2 ^ 1,10-phenanthroline 80 10 Ru (iCO) ^ PPh ^ 2,2'-bipyridine 65
Vertailuesimerkki 1 15 Muutamille muille esimerkkien IV ja VI mukaisissa koejärjestelyolosuhteis-sa Ru^(CO)j2/heterosyklinen emäs-systeemeille suoritetut katalysaattori-kokeet antoivat taulukon 3 mukaiset tulokset. Systeemit ovat homogeenisiä ja niiden aktiivisuudet muutamaa suuruusluokkaa alhaisemmat kuin Ru^CCO) j^/Mpyridiini-systeemin. Jotkut emäkset, kuten pyrrolidiini muo-20 dostavat kohtalaisia vedyntuottosysteemejä, mutta reagoivat hiilidioksidin kanssa, joten todellista katalyysiä ei tapahdu näissä systeemeissä.Comparative Example 1 15 A few other catalyst experiments performed on the Ru 2 (CO) 2 / heterocyclic base systems under the experimental setup conditions of Examples IV and VI gave the results shown in Table 3. The systems are homogeneous and have activities a few orders of magnitude lower than the Ru 2 CO 2 / pyridine system. Some bases, such as pyrrolidine, form moderate hydrogen production systems but react with carbon dioxide, so no real catalysis occurs in these systems.
Taulukko 3 25 Ru^(C0)^2:n katalyyttinen aktiivisuus vesikaasun siirtoreaktiossa eri emäsliuoksissaTable 3 Catalytic activity of Ru ^ (C0) ^ 2 in the water gas transfer reaction in different base solutions
Emäs/liuotin mol mol CO^ 30 mol kat. 24 h mol kat. 24 hBase / solvent mol mol CO 2 30 mol cat. 24 h mol cat. 24 h
Pyridiini 15 15Pyridine 15 15
Pyridiini/etoksietanoli 7 8 35 Pyridiini/DMSO 5 5Pyridine / ethoxyethanol 7 8 35 Pyridine / DMSO 5 5
Pyridiini/diglyymi 5 6Pyridine / diglyme 5 6
Piperidiini 10 0 li 69620 1________________________________Piperidine 10 0 li 69620 1________________________________
Emäs/liuotin mol mol CO^ mol kat. 24 h mol kat. 24 h 5 _________________________________________Base / solvent mol mol CO 2 mol cat. 24 h mol cat. 24 h 5 _______________________________________
Piperidiini/etoksietanoli 8 0Piperidine / ethoxyethanol 8 0
Piperidiini/DMSO 2 0 10 Piperidiini/diglyymi 10 0Piperidine / DMSO 2 0 10 Piperidine / diglyme 10 0
Trimetyyliamiini/diglyyrai 0 0Trimethylamine / diglycerol
Trietyyliamiini/diglyymi 4 1Triethylamine / diglyme 4 1
Trietyyliamiini/etoksietanoli 0 1Triethylamine / ethoxyethanol 0 1
Pyrrolidiini 117 0 15 Pyrrolidiini/diglyymi 2 0Pyrrolidine 117 0 15 Pyrrolidine / diglyme 2 0
Aniliini/diglyymi 0 7Aniline / diglyme 0 7
Pyrroli/diglyymi 0 3 2-dimetyyliaminoetanoli 7 4 2-dietyyliaminoetanoli 0 1 20 N,N-dietyylianiliini 4 0Pyrrole / diglyme 0 3 2-dimethylaminoethanol 7 4 2-diethylaminoethanol 0 1 20 N, N-diethylaniline 4 0
Dietanoliamiini 30 0Diethanolamine 30 0
Dietanoliamiini, kyllästetty 16 0Diethanolamine, saturated 16 0
Neokuproiini/diglyymi 18 20Neocuprine / diglyme 18 20
Etyleenidiamiini 48 0 25 Kinnoliini/diglyymi 0 0Ethylenediamine 48 0 25 Cinnoline / diglyme 0 0
Bentsyyliamiini/diglyymi 0 2 1,10-fenantroliini/diglyymi 13 13 30 35Benzylamine / diglyme 0 2 1,10-phenanthroline / diglyme 13 13 30 35
Claims (7)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI842175A FI69620C (en) | 1984-05-30 | 1984-05-30 | CATALYTIC CONTAINER FOR THE FRAME STATION OF VETGAS AND THREE METALS |
| NO852061A NO160245C (en) | 1984-05-30 | 1985-05-23 | CATALYST AND PROCEDURE FOR THE PREPARATION OF HYDROGEN GAS FROM CARBON MONOXIDE AND WATER. |
| DK232285A DK169124B1 (en) | 1984-05-30 | 1985-05-23 | Catalyst for producing hydrogen gas from carbon monoxide and water and process for producing hydrogen gas from carbon monoxide and water in the presence of a catalyst |
| US06/738,783 US4699775A (en) | 1984-05-30 | 1985-05-29 | Catalyst and method for producing hydrogen gas from carbon monoxide and water |
| CA000482696A CA1248933A (en) | 1984-05-30 | 1985-05-29 | Catalyst and procedure for producing hydrogen gas from carbon monoxide and water |
| JP60117622A JPS60261545A (en) | 1984-05-30 | 1985-05-30 | Catalyst and method for producing hydrogen from carbon monoxide and water |
| EP85303796A EP0163532B1 (en) | 1984-05-30 | 1985-05-30 | Catalyst and procedure for producing gas from carbon monoxide and water |
| DE8585303796T DE3579192D1 (en) | 1984-05-30 | 1985-05-30 | CATALYST AND METHOD FOR PRODUCING HYDROGEN FROM CARBON MONOXYDE AND WATER. |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI842175 | 1984-05-30 | ||
| FI842175A FI69620C (en) | 1984-05-30 | 1984-05-30 | CATALYTIC CONTAINER FOR THE FRAME STATION OF VETGAS AND THREE METALS |
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| Publication Number | Publication Date |
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| FI842175A0 FI842175A0 (en) | 1984-05-30 |
| FI69620B true FI69620B (en) | 1985-11-29 |
| FI69620C FI69620C (en) | 1986-03-10 |
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| FI842175A FI69620C (en) | 1984-05-30 | 1984-05-30 | CATALYTIC CONTAINER FOR THE FRAME STATION OF VETGAS AND THREE METALS |
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| Country | Link |
|---|---|
| US (1) | US4699775A (en) |
| EP (1) | EP0163532B1 (en) |
| JP (1) | JPS60261545A (en) |
| CA (1) | CA1248933A (en) |
| DE (1) | DE3579192D1 (en) |
| DK (1) | DK169124B1 (en) |
| FI (1) | FI69620C (en) |
| NO (1) | NO160245C (en) |
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| FI85849C (en) * | 1988-03-22 | 1992-06-10 | Neste Oy | FOERFARANDE FOER FRAMSTAELLNING AV ALKOHOLER OCH ALDEHYDER FRAON ALKENER OCH SYNTESGAS. |
| US4980145A (en) * | 1988-07-19 | 1990-12-25 | Air Products And Chemicals, Inc. | Liquid phase carbon monoxide shift process |
| FI84142C (en) * | 1990-01-16 | 1991-10-25 | Neste Oy | FOERFARANDE FOER FRAMSTAELLNING AV VATTENGAS- OCH HYDROFORMULERINGSKATALYT, EN MED FOERFARANDET FRAMSTAELLD KATALYT OCH ANVAENDNING AV KATALYTEN. |
| FI88116C (en) * | 1991-12-31 | 1993-04-13 | Neste Oy | FREQUENCY REFRIGERATION FOR HETEROGENE CATALYST |
| FI98603C (en) | 1995-11-09 | 1997-07-25 | Neste Oy | Process for producing catalytic converter for reaction of water gas and use of the catalytic converter |
| DE19834568A1 (en) * | 1998-07-31 | 2000-02-03 | Aventis Res & Tech Gmbh & Co | Bintered copper-ruthenium-supported catalysts with high sintering stability and process for their preparation |
| US7160534B2 (en) * | 2002-12-20 | 2007-01-09 | Honda Giken Kogyo Kabushiki Kaisha | Platinum-free ruthenium-cobalt catalyst formulations for hydrogen generation |
| US7700071B2 (en) * | 2004-01-23 | 2010-04-20 | Ovonic Battery Company, Inc. | Production of hydrogen via a base-facilitated reaction of carbon monoxide |
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| US3855307A (en) * | 1967-02-20 | 1974-12-17 | Monsanto Co | Catalysis |
| US3804914A (en) * | 1972-05-25 | 1974-04-16 | Phillips Petroleum Co | Ruthenium(ii)complexes as catalysts for selective hydrogenation of cyclic polyenes to cyclic monoenes |
| US4169853A (en) * | 1978-02-06 | 1979-10-02 | Texaco Development Corporation | Homogeneous ruthenium catalysts useful in the reduction of ortho-substituted nitroaromatics to amines |
| US4292242A (en) * | 1978-12-06 | 1981-09-29 | Sri International | Production of amines |
| US4344866A (en) * | 1979-10-31 | 1982-08-17 | Standard Oil Company | Carbonylation of olefinically unsaturated compounds |
| US4324695A (en) * | 1980-11-17 | 1982-04-13 | National Distillers & Chemical Corp. | Catalyst compositions of transition metal carbonyl complexes intercalcated with lamellar materials |
-
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1985
- 1985-05-23 NO NO852061A patent/NO160245C/en unknown
- 1985-05-23 DK DK232285A patent/DK169124B1/en not_active IP Right Cessation
- 1985-05-29 US US06/738,783 patent/US4699775A/en not_active Expired - Fee Related
- 1985-05-29 CA CA000482696A patent/CA1248933A/en not_active Expired
- 1985-05-30 DE DE8585303796T patent/DE3579192D1/en not_active Expired - Fee Related
- 1985-05-30 JP JP60117622A patent/JPS60261545A/en active Granted
- 1985-05-30 EP EP85303796A patent/EP0163532B1/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| DK169124B1 (en) | 1994-08-22 |
| NO852061L (en) | 1985-12-02 |
| US4699775A (en) | 1987-10-13 |
| DK232285A (en) | 1985-12-01 |
| CA1248933A (en) | 1989-01-17 |
| NO160245C (en) | 1991-05-22 |
| FI842175A0 (en) | 1984-05-30 |
| EP0163532A2 (en) | 1985-12-04 |
| DK232285D0 (en) | 1985-05-23 |
| FI69620C (en) | 1986-03-10 |
| JPS60261545A (en) | 1985-12-24 |
| JPH0530502B2 (en) | 1993-05-10 |
| EP0163532A3 (en) | 1987-05-27 |
| NO160245B (en) | 1988-12-19 |
| DE3579192D1 (en) | 1990-09-20 |
| EP0163532B1 (en) | 1990-08-16 |
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